EP0131848B1 - Process for the elimination of foreign substances from the circulation of material in the electrothermic preparation of yellow phosphorus - Google Patents

Process for the elimination of foreign substances from the circulation of material in the electrothermic preparation of yellow phosphorus Download PDF

Info

Publication number
EP0131848B1
EP0131848B1 EP84107760A EP84107760A EP0131848B1 EP 0131848 B1 EP0131848 B1 EP 0131848B1 EP 84107760 A EP84107760 A EP 84107760A EP 84107760 A EP84107760 A EP 84107760A EP 0131848 B1 EP0131848 B1 EP 0131848B1
Authority
EP
European Patent Office
Prior art keywords
slag
dust
ground
granules
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP84107760A
Other languages
German (de)
French (fr)
Other versions
EP0131848A3 (en
EP0131848A2 (en
Inventor
Karl Röttgen
Joachim Dr. Stendel
Herbert Dr. Diskowski
Jens Dr. Tiedemann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0131848A2 publication Critical patent/EP0131848A2/en
Publication of EP0131848A3 publication Critical patent/EP0131848A3/en
Application granted granted Critical
Publication of EP0131848B1 publication Critical patent/EP0131848B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/02Preparation of phosphorus
    • C01B25/027Preparation of phosphorus of yellow phosphorus

Definitions

  • the present invention relates to a process for discharging foreign substances, in particular zinc, from the material cycle in the production of yellow phosphorus in an electrothermal furnace, wherein from the furnace charged with phosphate pellets, coke and gravel, ferrophosphorus and a slag consisting essentially of calcium metasilicate in molten form and dust-containing gas mixture consisting essentially of carbon monoxide and phosphorus vapor is withdrawn, and the dust is mixed with water to form a dust mash after electrostatic separation from the gas mixture, and raw phosphate with a mixture of dust mash under a clay mash is processed with the aid of a pelletizer to give shaped articles which are annealed to phosphate pellets on a sintering device.
  • ferrophosphorus can optionally be worked up to obtain the vanadium contained in it or used in the production of phosphorus-rich alloys
  • the slag is a relatively worthless material that is sent to landfills (see “Ullmanns Encyklopadie der Technische Chemie", 4th edition, 1979 , Pages 288 to 295).
  • the zinc concentration in the material cycle of the phosphor furnace depends primarily on the zinc content of the raw materials, in particular of the raw phosphate, about 4% of the zinc passing through the phosphor furnace being discharged with the slag and the ferrophosphorus.
  • the zinc phosphides which are formed from the reduced zinc in the phosphorus vapor-saturated furnace atmosphere, can be sublimed and condense at temperatures of less than 1000 ° C in the colder areas of the furnace, for example, with the formation of incrustations on the furniture mixture. The pourability of the furniture mix is reduced by the incrustations.
  • Abrasion-friendly phosphate pellets lead to dust monitors in the phosphor furnace, by means of which the gas permeability of the furniture mixture and the heat exchange between the gas mixture formed in the phosphor furnace and the furniture mixture is reduced. Compared to the normal operation of the phosphor furnace, this leads to an increase in the temperature of the gas mixture leaving the phosphor furnace, which impairs the functionality of the electrostatic precipitator and ultimately limits the electrical power consumption of the phosphor furnace.
  • This is achieved according to the invention by grinding part of the slag; that the ground slag is processed with at least part of the dust mash with the aid of a granulating device to form a granulate; and that you dry the granules.
  • the method according to the invention it is possible, by discharging a suitable proportion of the electrostatically separated dust, to specifically lower the foreign substance concentration in the material circuit of the phosphor furnace from the amount of foreign matter introduced with the raw materials, in particular with the raw phosphate. Therefore, when using the method according to the invention, it is also possible, for example, to use zinc-rich raw phosphates in the electrothermal phosphor furnace without interfering with the operation of the furnace.
  • the process according to the invention improves the economic viability of producing yellow phosphorus in an electrothermal furnace by, on the one hand, saving the additional consumption of electrical current and coke required for reducing the foreign substances discharged, and on the other hand increasing the yield of yellow phosphorus, since the zinc is phosphorus as phosphides binds, the phosphorus being lost in elemental form during hydrolysis outside the electrothermal furnace or during oxidation during sintering.
  • the method according to the invention can be carried out with the aid of an arrangement consisting of a mill, granulating device and sintering device, as is also customary for the production of phosphate pellets.
  • 10 to 50% by weight of compounds containing calcium oxide, based on filter cake can be added to the mixture of filter cake and slag.
  • a weighed amount 1 of phosphate pellets 2, coke 3 and gravel 4 is introduced into the electrothermal reduction furnace 5.
  • slag 6 and ferrophosphorus 7 are drawn off in molten form, while a line 8 leads off from the cover of the furnace 5, via which a dust-containing gas mixture consisting essentially of carbon monoxide and phosphorus vapor is fed to an electrical separator 9.
  • the dust-free gas mixture leaves the electrostatic precipitator 9 via a line 10 leading to condensation, while the dust emerges at the bottom of the electrostatic precipitator 9 and is introduced into a stirred tank 12 containing water via a submerged line 11.
  • the dust mash containing the foreign substances flows via a line 13 after mixing with clay mash from the line 14 to the turntable 15.
  • Crude phosphate is fed to the mill 17 via the transport member 16.
  • the ground raw phosphate passes through a transport member 18 to the turntable 15, on which it is converted into moldings with the mixture of dust mash and clay mash as a binder.
  • the moldings are fed to the sintering device 20 via the transport member 19 and are first dried therein and then annealed to form raw phosphate pellets.
  • part of the dust mash containing the foreign substances is removed from line 13 and fed to a turntable 22 via line 21.
  • Ground slag is placed on the turntable 22 via a transport member 23 and processed into granules by means of the dust mash from the line 21.
  • the slag has previously been ground in a mill 24, the grinder 24 being loaded with granular slag via transport elements (25, 26).
  • the granulate is fed via a transport member 27 to a sintering device 28, in which it is either only dried and fed again to the mill 24 via the transport members (29, 26) or it is dried and annealed in the sintering device 28 and transferred to the via a transport member 30 Given landfill.
  • part of the dust mash containing the foreign substances is discharged from line 13 and partly fed via line 21 to a turntable 22.
  • a line 31 branches off from line 21, through which a further part of the dust mash is fed to a filter 32.
  • the filter cake from the filter 32 is conveyed through a transport member 34 into a transport member 25, through which granular slag is brought in.
  • the mixture of filter cake and granular slag falls on a transport member 26, which is connected to a mill 24 in terms of material flow.
  • the ground mixture of filter cake and slag leaving the mill 24 is fed to the turntable 22 via a transport member 23, on which it is processed into granules with the aid of dust mash emerging from the line 21.
  • the granulate is fed via a transport member 27 to a sintering device 28, in which it may be either only dried and fed to the mill 24 again via the transport members (29, 26) after admixing further filter cake via the transport members (34, 35) or it will be dried in the sintering device 28 and annealed to pellets, which are transferred to the landfill via a transport member 30.
  • crude phosphate as the raw material for the furnace was processed into phosphate pellets with the sintering line above the dashed line (mill 17, turntable 15, sintering device 20).
  • the sintering line below the dashed line was used to discharge dust mash according to the invention in a depositable form.
  • the cooling gas obtained at the sintering device 20 at approximately 440 ° C. was used to dry the granules in the sintering device 28.
  • the 80 t of slag were sufficient to process 140 m 3 (corresponding to 175 t) of dust mash.
  • a ground mixture of 40 kg of phosphorus furnace slag and 10 kg of limestone powder was granulated with dust mash in a granulating drum of 250 l content and dried at 110 ° C.
  • the granules were ground and again granulated with further dust mash and dried at 110 ° C. This cycle was carried out a total of 14 times.
  • the dried granules were annealed at 800 ° C to form pellets.
  • the pellets had a zinc content of 5.8%.
  • the Dust mash used had a density of 1.2 kg / l, a solids content of about 30% and a solids-based zinc content of 13%.
  • Example 2 In the pelletizing drum used in Example 2, 40 kg of ground phosphor furnace slag and. 29.6 kg filter cake, which had been obtained by filtration of dust mash, filled and mixed. The mixture was granulated using dust mash. The granules were dried at 110 ° C and then annealed at 800 ° C. The resulting pellets had a zinc content of 6.1%.
  • the dust mash used had a density of 1.2 kg / l, a solids content of about 30% and a zinc content of 13% based on the solids.
  • the pellets obtained according to Examples 1 to 3 were subjected to an elution test with distilled water (see DIN 38 414 (draft) part 4, April 1983). The analysis of the three eluates is shown in the table.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Description

Die vorliegende Erfindung betrifft ein Verfahren zum Ausschleusen von Fremdstoffen, insbesondere Zink, aus dem Materialkreislauf bei der Herstellung von gelbem Phosphor im elektrothermischen Ofen, wobei aus dem mit Phosphatpellets, Koks und Kies beschickten Ofen Ferrophosphor und eine im wesentlichen aus Calciummetasilikat bestehende Schlacke in schmelzflüssiger Form sowie Staub enthaltendes, im wesentlichen aus Kohlenmonoxid und Phosphordampf bestehendes Gasgemisch abgezogen wird, und wobei der Staub nach elektrostatischer Abtrennung vom Gasgemisch mit Wasser zu einer Staubmaische angerührt wird, und wobei Rohphosphat mit einer Mischung aus Staubmaische under einer Tonmaische mit Hilfe einer Granuliereinrichtung zu Formlingen verarbeitet wird, welche auf einer Sintereinrichtung zu Phosphatpellets geglüht werden.The present invention relates to a process for discharging foreign substances, in particular zinc, from the material cycle in the production of yellow phosphorus in an electrothermal furnace, wherein from the furnace charged with phosphate pellets, coke and gravel, ferrophosphorus and a slag consisting essentially of calcium metasilicate in molten form and dust-containing gas mixture consisting essentially of carbon monoxide and phosphorus vapor is withdrawn, and the dust is mixed with water to form a dust mash after electrostatic separation from the gas mixture, and raw phosphate with a mixture of dust mash under a clay mash is processed with the aid of a pelletizer to give shaped articles which are annealed to phosphate pellets on a sintering device.

Es ist bekannt, in einem elektrothermischen Ofen aus einer aus Phosphatpellets, Koks und Kies bestehenden Möllermischung gelben Phosphor herzustellen. Dabei wird aus dem Ofen ein staubhaltiges, im wesentlichen Phosphordampf und Kohlenmonoxid enthaltendes Gasgemisch sowie in schmelzflüssiger Form Ferrophosphor und eine im wesentlichen aus Calciummetasilikat bestehende Schlacke abgezogen. Das staubhaltige Gasgemisch wird in einem Elektroabscheider entstaubt, wobei der am Boden des Elektroabscheiders ausgetragene Staub in einem nachgeschalteten Behälter mit Wasser zu einer Staubmaische angerührt wird. Die Staubmaische dient zusammen mit einer Tonmaische als Bindemittel für die Agglomerierung von Rohphosphat auf Drehtellern mit anschließender Calcinierung zu Phosphatpellets. Während Ferrophosphor gegebenenfalls zur Gewinnung des in ihm enthaltenen Vanadiums aufgearbeitet oder bei der Herstellung von phosphorreichen Legierungen benutzt werden kann, stellt die Schlacke ein relativ wertloses Material dar, welches Deponien zugeführt wird (vergleiche "Ullmanns Encyklopädie der technischen Chemie", 4. Auflage, 1979, Seiten 288 bis 295).It is known to produce yellow phosphorus in an electrothermal furnace from a furniture mixture consisting of phosphate pellets, coke and gravel. A gas mixture containing dust, essentially containing phosphorus vapor and carbon monoxide, as well as in the molten form ferrophosphorus and a slag consisting essentially of calcium metasilicate, are drawn off from the furnace. The dust-containing gas mixture is dedusted in an electrical separator, the dust discharged at the bottom of the electrical separator being mixed with water in a downstream container to form a dust mash. The dust mash, together with a clay mash, serves as a binder for the agglomeration of raw phosphate on turntables with subsequent calcination to form phosphate pellets. While ferrophosphorus can optionally be worked up to obtain the vanadium contained in it or used in the production of phosphorus-rich alloys, the slag is a relatively worthless material that is sent to landfills (see "Ullmanns Encyklopadie der Technische Chemie", 4th edition, 1979 , Pages 288 to 295).

Bei der Rückführung des elektrostatisch aus dem Gasgemisch abgetrennten Stabues in den Materialkreislauf des elektrothermischen Phosphorofens erfolgt eine Anreicherung verschiedener Fremdstoffe wie Zink, Cadmium und anderer Schwermetalle, aber auch wirtschaftlich interessanter Metalle wie Gallium und Germanium. Dabei liegen die Fremdstoffe teilweise als Phosphide vor, beispielsweise Zink als ZnP2 oder Zn3Pz.When the stabilizer separated electrostatically from the gas mixture is returned to the material cycle of the electrothermal phosphor furnace, various foreign substances such as zinc, cadmium and other heavy metals, but also economically interesting metals such as gallium and germanium, are accumulated. The foreign substances are partially present as phosphides, for example zinc as ZnP 2 or Zn 3 P z .

Die Auswirkung eines hohen Fremdstoffgehaltes im Materialkreislauf des elektrothermischen Phosphorofens sei anhand des Zinkumlaufes erläutert. Dabei ist zu berücksichtigen, daß die ZinkKonzentration im Materialkreislauf des Phosphorofens in erster Linie vom Zink-Gehalt der Rohstoffe, insbesondere des Rohphosphates abhängt, wobei etwa 4% des den Phosphorofen durchlaufenden Zinks mit der Schlacke und dem Ferrophosphor ausgeschleust wird. Die Phosphide des Zinks, welche sich aus dem reduzierten Zink in der phosphordampfgesättigten Ofenatmosphäre bilden, sind sublimierbar und kondensieren bei Temperaturen von weniger als 1000°C in den kälteren Bereichen im Ofen, beispielsweise unter Bildung von Verkrustungen auf der Möllermischung. Durch die Verkrustungen wird die Rieselfähigkeit der Möllermischung herabgesetzt. Von der Rieselfähigkeit der Möllermischung und ihrer Gasdurchlässigkeit aber hängt es ab, ob ein guter Wärmeaustausch zwischen den aufwärts strömenden Gasgemisch aus Phosphordampf und Kohlenmonoxid und der von oben nachrutschenden relativ kalten Möllermischung erfolgt. Strömt das Gasgemisch zu heiß aus dem Phosphorofen ab, so werden einerseits die Ofendecke und darin angeordnete Einrichtungen gefährdet und andererseits läßt die Wirksamkeit des Elektroabscheiders nach. Schließlich tritt beim Eintrag des mit 400 bis 600°C aus dem Elektroabscheider ausgetragenen Staubes in Wasser und bei der Gewinnung der Staubmaische Hydrolyse eines Teiles der Zinkphosphide ein. Dadurch wird die Staubmaische hochviskos und ist schlect weiterzuverarbeiten. Bei Eintrag von Ton in eine solche Staubmaische erfolgt eine weitere Verdickung, so daß sich der Zusatz von Ton zu einer Hydrolyseprodukte der Zinkphosphide enthaltenen Staubmaische verbietet. Bei der Verwendung einer Staubmaische ohne Tonzusatz als Granuliermaische für Rohrphosphat ist aber nicht sichergestellt, daß einerseits die Bindefähigkeit bei der Granulation des Rohphosphates zu Formlingen und andererseits die Abriebfestigkeit der aus den Formlingen durch Glühen hergestellten Phosphatpellets ausreichend ist. Abriebfreudige Phosphatpellets führen aber im Phosphorofen zu Staubwächten, durch welche die Gasdurchlässigkeit der Möllermischung und der Wärmeaustausch zwischen dem im Phosphorofen gebildetem Gasgemisch under der Möllermischung herabgesetzt wird. Gegenüber dem normalen Gang des Phosphorfens tritt dadurch eine Erhöhung der Temperatur des den Phosphorofen verlassenden Gasgemisches ein, wodurch die Funktionsfähigkeit des Elektroabscheiders beeinträchtigt und letztlich die elektrische Leistungsaufnahme des Phosphorofens begrenzt wird.The effect of a high foreign matter content in the material cycle of the electrothermal phosphor furnace is explained using the zinc circulation. It should be taken into account that the zinc concentration in the material cycle of the phosphor furnace depends primarily on the zinc content of the raw materials, in particular of the raw phosphate, about 4% of the zinc passing through the phosphor furnace being discharged with the slag and the ferrophosphorus. The zinc phosphides, which are formed from the reduced zinc in the phosphorus vapor-saturated furnace atmosphere, can be sublimed and condense at temperatures of less than 1000 ° C in the colder areas of the furnace, for example, with the formation of incrustations on the furniture mixture. The pourability of the furniture mix is reduced by the incrustations. However, it depends on the pourability of the furniture mixture and its gas permeability whether there is a good heat exchange between the upward flowing gas mixture of phosphorus vapor and carbon monoxide and the relatively cold furniture mixture sliding down from above. If the gas mixture flows out of the phosphor furnace too hot, on the one hand the furnace ceiling and the devices arranged therein are endangered and on the other hand the effectiveness of the electrostatic precipitator deteriorates. Finally, when the dust discharged from the electrostatic precipitator at 400 to 600 ° C. is introduced into water and when the dust mash is obtained, hydrolysis of some of the zinc phosphides occurs. This makes the dust mash highly viscous and is difficult to process further. When clay is introduced into such a dust mash, there is a further thickening, so that the addition of clay to a hydrolysis product of the zinc phosphides contained dust mash is prohibited. When using a dust mash without added clay as a granulating mash for tubular phosphate, however, it is not ensured that, on the one hand, the binding capacity during the granulation of the crude phosphate into shaped articles and, on the other hand, the abrasion resistance of the phosphate pellets produced from the shaped articles by annealing is sufficient. Abrasion-friendly phosphate pellets, however, lead to dust monitors in the phosphor furnace, by means of which the gas permeability of the furniture mixture and the heat exchange between the gas mixture formed in the phosphor furnace and the furniture mixture is reduced. Compared to the normal operation of the phosphor furnace, this leads to an increase in the temperature of the gas mixture leaving the phosphor furnace, which impairs the functionality of the electrostatic precipitator and ultimately limits the electrical power consumption of the phosphor furnace.

Es ist daher Aufgabe der vorliegenden Erfindung, ein Verfahren zum Ausschleusen von Fremdstoffen, insbesondere Zink, aus dem Materialkreislauf bei der Herstellung von gelbem Phosphor im elektrothermischen Ofen anzugeben, bei welchem ein die Fremdstoffe in unlöslicher Form enthaltendes, deponierfähiges Produkt anfällt. Das wird erfindungsgemäß dadurch erreicht, daß man einen Teil der Schlacke mahlt; daß man die gemahlene Schlacke mit mindestens einem Teil der Staubmaische mit Hilfe einer Granuliereinrichtung zu einem Granulat verarbeitet; und daß man das Granulat trocknet.It is therefore an object of the present invention, a method for discharging foreign substances, in particular zinc to provide from the circulation of material in the production of yellow phosphorus in the electro-thermal furnace, in which a foreign matter in insoluble form is obtained containing, deponier f ähiges product. This is achieved according to the invention by grinding part of the slag; that the ground slag is processed with at least part of the dust mash with the aid of a granulating device to form a granulate; and that you dry the granules.

Das Verfahren gemäß der Erfindung kann weiterhin wahlweise auch noch dadurch ausgestaltet sein, daß

  • a) man das getrocknete Granulat erneut mahlt und das Mahlgut mit weitere Staubmaische granuliert und trocknet;
  • b) man dem Mahlgut kalziumoxidhaltige Verbindungen, vorzugsweise Kalksteinmehl und/oder Hydratkalk, zusetzt;
  • c) man das getrocknete und gemahlene Granulat und Staubmaische im Gewichtsverhältnis von 6:1 bis 7:1 granuliert;
  • d) man dem zum Mahlen vorgesehenen Teil der Schlacke durch Filtrieren von Staubmaische erhaltenen Filterkuchen zusetzt;
  • e) das Gewichtsverhältnis von Schlacke zu Filterkuchen von 0,5:1 bis 10:1 beträgt;
  • f) man dem Gemisch aus Schlacke und Filterkuchen kalziumoxidhaltige Verbindungen, vorzugsweise Kalksteinsplit, zusetzt;
  • g) man die Schlacke bzw. das Gemisch aus Schlacke und Filterkuchen bzw. das Gemisch aus Schlacke, Filterkuchen und kalziumoxidhaltigen Verbindungen auf Korngrößen von 80% <100 um mahlt;
  • h) man das Granulat bei Temperaturen von 80 bis 150°C trocknet;
  • i) man die gemahlene Schlacke bzw. das gemahlene Gemisch aus Schlacke und Filterkuchen bzw. das gemahlene Gemisch aus Schlacke, Filterkuchen und kalziumoxidhaitigen Verbindungen mit Staubmaische im Gewichtsverhältnis von 5:1 bis 7:1 zum Granulat verarbeitet;
  • j) man das getrocknete Granulat unter Bildung von Pellets glüht; und daß man die Pellets gemeinsam mit der übrigen, nicht behandelten Schlacke einer Deponie zuführt;
  • k) man das getrocknete Granulat bei Temperaturen von 500 bis 800°C glüht.
The method according to the invention can furthermore optionally also be designed in that
  • a) the dried granules are ground again and the ground material is granulated with further dust mash and dried;
  • b) calcium oxide-containing compounds, preferably limestone powder and / or hydrated lime, are added to the millbase;
  • c) the dried and ground granules and dust mash are granulated in a weight ratio of 6: 1 to 7: 1;
  • d) filter cake obtained by grinding dust mash is added to the part of the slag intended for grinding;
  • e) the weight ratio of slag to filter cake is from 0.5: 1 to 10: 1;
  • f) calcium oxide-containing compounds, preferably limestone split, are added to the mixture of slag and filter cake;
  • g) the slag or the mixture of slag and filter cake or the mixture of slag, filter cake and compounds containing calcium oxide are ground to particle sizes of 80% <100 μm;
  • h) drying the granules at temperatures from 80 to 150 ° C;
  • i) the ground slag or the ground mixture of slag and filter cake or the ground mixture of slag, filter cake and calcium oxide-containing compounds is processed with dust mash in a weight ratio of 5: 1 to 7: 1 to the granules;
  • j) the dried granules are annealed to form pellets; and that the pellets are taken to a landfill together with the remaining, untreated slag;
  • k) the dried granules are annealed at temperatures of 500 to 800 ° C.

Mit dem Verfahren gemäß der Erfindung ist es möglich, durch Ausschleusen eines geeigneten Anteils des elektrostatisch abgeschiedenen Staubes die Fremdstoffkonzentration im Materialkreislauf des Phosphorofens von der mit den Rohstoffen, insbesondere mit dem Rohphosphat, eingebrachten Fremdstoffmenge gezielt abzusenken. Daher ist es bei Anwendung des Verfahrens gemäß der Erfindung beispielsweise auch möglich, zinkreiche Rohphosphate im elektrothermischen Phosphorofen ohne Störungen im Betrieb des Ofens einzusetzen.With the method according to the invention it is possible, by discharging a suitable proportion of the electrostatically separated dust, to specifically lower the foreign substance concentration in the material circuit of the phosphor furnace from the amount of foreign matter introduced with the raw materials, in particular with the raw phosphate. Therefore, when using the method according to the invention, it is also possible, for example, to use zinc-rich raw phosphates in the electrothermal phosphor furnace without interfering with the operation of the furnace.

Durch das erfindungsgemäße Verfahren wird die Wirtschaftlichkeit der Herstellung von gelbem Phosphor im elektrothermischen Ofen verbessert, indem einerseits der für die Reduktion der ausgeschleusten Fremdstoffe erforderliche Mehrverbrauch an elektrischem Strom und Koks eingespart und andererseits die Ausbeute an gelbem Phosphor erhöht wird, da das Zink Phosphor als Phosphide bindet, wobei der Phosphor bei der Hydrolyse außerhalb des elektrothermischen Ofens oder bei der Oxidation während der Sinterung in elementarer Form verlorengeht.The process according to the invention improves the economic viability of producing yellow phosphorus in an electrothermal furnace by, on the one hand, saving the additional consumption of electrical current and coke required for reducing the foreign substances discharged, and on the other hand increasing the yield of yellow phosphorus, since the zinc is phosphorus as phosphides binds, the phosphorus being lost in elemental form during hydrolysis outside the electrothermal furnace or during oxidation during sintering.

Das Verfahren gemäß der Erfindung kann mit Hilfe einer aus Mühle, Granuliereinrichtung und Sintereinrichtung bestehenden Anordnung durchgeführt werden, wie sie auch für die Herstellung von Phosphatpellets gebräuchlich ist.The method according to the invention can be carried out with the aid of an arrangement consisting of a mill, granulating device and sintering device, as is also customary for the production of phosphate pellets.

Beim erfindungsgemäßen Verfahren ist es zweckmäßig, das getrocknete Granulat nicht sofort zu glühen und auf die Deponie zu geben, sondern erneut zu mahlen und mit weiterer Staubmaische auf dem Drehteller zu Granulat zu verarbeiten und zu trocknen: Dabei kann dieser Vorgang gegebenenfalls so oft wiederholt werden, bis eine gewünschte Menge Feststoff aus der Staubmaische an Schlacke gebunden ist. Dadurch erhält man ein mit Verunreinigungen hoch angereichertes Granulat, wobei im Laufe der Anreicherung auch noch Kalksteinmehl oder Hydratkalk zugesetzt werden kann, um das bei der Bildung unlöslicher Phosphate verbrauchte CaO zu ergänzen, so daß die Matrix ihren neutralen bis alkalischen Charakter behält. Ist das Granulat in erwünschter Weise angereichert, so wird es nach der letzten Trocknung geglüht.In the method according to the invention, it is expedient not to glow the dried granules immediately and to put them in the landfill, but to grind them again and to process and dry them with additional dust mash on the turntable into granules: this process can be repeated as often as necessary until a desired amount of solid matter from the dust mash is bound to slag. This gives granules which are highly enriched with impurities, and in the course of the enrichment it is also possible to add limestone powder or hydrated lime in order to supplement the CaO consumed in the formation of insoluble phosphates, so that the matrix retains its neutral to alkaline character. If the granulate is enriched in the desired way, it is annealed after the last drying.

Beim Verfahren gemäß der Erfindung kann eine erhebliche Menge Energie sowie Aufarbeitungszeit und Kapazität der Einrichtung eingespart werden, wenn man den größten Teil der aus dem Phosphor-Produktionsprozeß abgezweigten Staubmaische zunächst durch Filtrieren in einem Filterkuchen und ein Filtrat auftrennt. Während das Filtrat in den Phosphor-Produktionsprozeß zurückgeführt wird, wird der Filterkuchen gemeinsam mit der Schlacke vermahlen. Nach anschließender Granulierung des gemahlenen Filterkuchen - Schlacken - Gemisches mit Hilfe von Staubmaische sowie Trocknen und Glühen des Granulates erhält man in einem einzigen Schritt Pellets mit einem Staubmaische-Anteil von beispielsweise 40 Gewichts% und einem Zinkgehalt von mehr als 3 Gewichts%. Diese Pellets können unmittelbar gemeinsam mit unbehandelter Schlacke deponiert werden.In the method according to the invention, a considerable amount of energy as well as the processing time and the capacity of the device can be saved if the majority of the dust mashes branched off from the phosphorus production process are first separated by filtering in a filter cake and a filtrate. While the filtrate is being returned to the phosphorus production process, the filter cake is ground together with the slag. After subsequent granulation of the ground filter cake - slag - mixture with the aid of dust mash and drying and annealing of the granules, pellets with a dust mash fraction of, for example, 40% by weight and a zinc content of more than 3% by weight are obtained in a single step. These pellets can be deposited directly together with untreated slag.

Beim erfindungsgemäßen Verfahren können dem Gemisch von Filterkuchen und Schlacke 10 bis 50 Gewichts% kalziumoxidhaltige Verbindungen, bezogen auf Filterkuchen, zugesetzt werden.In the process according to the invention, 10 to 50% by weight of compounds containing calcium oxide, based on filter cake, can be added to the mixture of filter cake and slag.

Das Verfahren gemäß der Erfindung sei anhand der beigefügten Zeichnung erläutert, in deren Blockschemata oberhalb der gestrichelten waagerechten Linie der Materialkreislauf bei der Herstellung von gelbem Phosphor im elektrothermischen Ofen nach dem Stand der Technik dargestellt ist, während unterhalb dieser Linie die erfindungsgemäße Ausschleusung von Fremdstoffen wiedergegeben ist. Dabei zeigen

  • Figur 1 die Granulierung von gemahlener Schlacke mit Staubmaische und
  • Figur 2 die Granulierung eines gemahlenen Gemisches von durch Filtration von Staubmaische erhaltenem Filterkuchen und Schlacke mit Staubmaische mit jeweils anschließendem Trocknen und Glühen unter Bildung von Pellets.
The process according to the invention will be explained with reference to the accompanying drawing, in whose block diagrams above the dashed horizontal line the material cycle for the production of yellow phosphorus in the electrothermal furnace according to the prior art is shown, while below this line the discharge of foreign substances according to the invention is shown . Show
  • Figure 1 shows the granulation of ground slag with dust mash and
  • FIG. 2 shows the granulation of a ground mixture of filter cake and slag obtained by filtering dust mash with dust mash, each with subsequent drying and annealing to form pellets.

Eine abgewogene Menge 1 von Phosphatpellets 2, Koks 3 und Kies 4 wird in den elektrothermischen Reduktionsofen 5 eingebracht. Im unteren Bereich des Ofens 5 wird in schmelzflüssiger Form Schlacke 6 und Ferrophosphor 7 abgezogen, während vom Deckel des Ofens 5 eine Leitung 8 abgeht, über welche ein staubhaltiges, im wesentlichen aus Kohlenmonoxid und Phosphordampf bestehendes Gasgemisch einem Elektroabscheider 9 zugeführt wird. Den Elektroabscheider 9 verläßt das staubfreie Gasgemisch über eine zur Kondensation führende Leitung 10, während der Staub am Boden des Elektroabscheiders 9 austritt und über eine abgetauchte Leitung 11 in einen Waser enthaltenden Rührbehälter 12 eingetragen wird. Vom Boden des Rührbehälters 12 fließt die die Fremdstoffe enthaltende Staubmaische über eine Leitung 13 nach Vermischung mit Tonmaische aus der Leitung 14 dem Drehteller 15 zu. Rohphosphat wird über das Transportorgan 16 der Mühle 17 zugeführt. Das gemahlene Rohphosphat gelangt über ein Transportorgan 18 auf den Drehteller 15, auf welchem es mit der Mischung von Staubmaische und Tonmaische als Bindemittel in Formlinge überführt wird. Die Formlinge werden über das Transportorgan 19 der Sintereinrichtung 20 zugeführt und darin zunächst getrocknet und anschließend zu Rohphosphatpellets geglüht.A weighed amount 1 of phosphate pellets 2, coke 3 and gravel 4 is introduced into the electrothermal reduction furnace 5. In the lower region of the furnace 5, slag 6 and ferrophosphorus 7 are drawn off in molten form, while a line 8 leads off from the cover of the furnace 5, via which a dust-containing gas mixture consisting essentially of carbon monoxide and phosphorus vapor is fed to an electrical separator 9. The dust-free gas mixture leaves the electrostatic precipitator 9 via a line 10 leading to condensation, while the dust emerges at the bottom of the electrostatic precipitator 9 and is introduced into a stirred tank 12 containing water via a submerged line 11. From the bottom of the stirred container 12, the dust mash containing the foreign substances flows via a line 13 after mixing with clay mash from the line 14 to the turntable 15. Crude phosphate is fed to the mill 17 via the transport member 16. The ground raw phosphate passes through a transport member 18 to the turntable 15, on which it is converted into moldings with the mixture of dust mash and clay mash as a binder. The moldings are fed to the sintering device 20 via the transport member 19 and are first dried therein and then annealed to form raw phosphate pellets.

Nach Figur 1 wird ein Teil der die Fremdstoffe enthaltenden Staubmaische aus der Leitung 13 ausgeschleust und über eine Leitung 21 einem Drehteller 22 zugeführt. Auf den Drehteller 22 wird über ein Transportorgan 23 gemahlene Schlacke aufgegeben und mit Hilfe der Staubmaische aus der Leitung 21 zu einem Granulat verarbeitet. Die Schlacke ist vorher in einer Mühle 24 gemahlen worden, wobei die Mühle 24 über Transportorgane (25, 26) mit körniger Schlacke beaufschlagt wurde. Das Granulat wird über ein Transportorgan 27 einer Sintereinrichtung 28 zugeführt, in welcher es entweder nur getrocknet und über die Transportorgane (29, 26) erneut der Mühle 24 zugeführt wird oder es wird in der Sintereinrichtung 28 getrocknet und geglüht und über ein Transportorgan 30 auf die Deponie gegeben.According to FIG. 1, part of the dust mash containing the foreign substances is removed from line 13 and fed to a turntable 22 via line 21. Ground slag is placed on the turntable 22 via a transport member 23 and processed into granules by means of the dust mash from the line 21. The slag has previously been ground in a mill 24, the grinder 24 being loaded with granular slag via transport elements (25, 26). The granulate is fed via a transport member 27 to a sintering device 28, in which it is either only dried and fed again to the mill 24 via the transport members (29, 26) or it is dried and annealed in the sintering device 28 and transferred to the via a transport member 30 Given landfill.

Nach Figur 2 wird ein Teil der die Fremdstoffe enthaltenden Staubmaische aus der Leitung 13 ausgeschleust und teilweise über eine Leitung 21 einem Drehteller 22 zugeführt. Von der Leitung 21 zweigt eine Leitung 31 ab, durch welche ein weiterer Teil der Staubmaische einem Filter 32 zugeführt wird. Während das Filtrat von dem Filter 32 durch eine Leitung 33 in den Rührbehälter 12 zurückgeführt wird, wird der Filterkuchen von Filter 32 durch ein Transportorgan 34 in ein Transportorgan 25 gefördert, durch welches körnige Schlacke herangeschafft wird. Die Mischung von Filterkuchen und körniger Schlacke fällt auf ein Transportorgan 26, weiches mit einer Mühle 24 materialströmungsmäßig verbunden ist. Das die Mühle 24 verlassende gemahlene Gemisch von Filterkuchen und Schlacke wird über ein Transportorgan 23 dem Drehteller 22 zugeführt, auf welchem es mit Hilfe von aus der Leitung 21 austretender Staubmaische zu einem Granulat verarbeitet wird. Das Granulat wird über ein Transportorgan 27 einer Sintereinrichtung 28 zugeführt, in welcher es gegebenenfalls entweder nur getrocknet und über die Transportorgane (29, 26) nach Zumischung von weiterem Filterkuchen über die Transportorgane (34, 35) erneut der Mühle 24 zugeführt wird oder es wird in der Sintereinrichtung 28 getrocknet und zu Pellets geglüht, welche über ein Transportorgan 30 auf die Deponie gegeben werden.According to FIG. 2, part of the dust mash containing the foreign substances is discharged from line 13 and partly fed via line 21 to a turntable 22. A line 31 branches off from line 21, through which a further part of the dust mash is fed to a filter 32. While the filtrate is returned from the filter 32 through a line 33 into the stirred tank 12, the filter cake from the filter 32 is conveyed through a transport member 34 into a transport member 25, through which granular slag is brought in. The mixture of filter cake and granular slag falls on a transport member 26, which is connected to a mill 24 in terms of material flow. The ground mixture of filter cake and slag leaving the mill 24 is fed to the turntable 22 via a transport member 23, on which it is processed into granules with the aid of dust mash emerging from the line 21. The granulate is fed via a transport member 27 to a sintering device 28, in which it may be either only dried and fed to the mill 24 again via the transport members (29, 26) after admixing further filter cake via the transport members (34, 35) or it will be dried in the sintering device 28 and annealed to pellets, which are transferred to the landfill via a transport member 30.

Beispiel 1example 1

Zwei elektrothermische Öfen zur Herstellung von gelbem Phosphor mit einer durchschnittlichen Gesamtleistung von 75 MW setzten pro Tag 1100 t Rohphosphat durch, welches als Fremdstoff u. a. 7,5 10-3% Zink enthielt. Aus dem im wesentlichen aus Kohlenmonoxid und Phosphordampf bestehenden Gasgemisch wurde durch den Elektroabscheider soviel Staub abgeschieden, daß täglich Staubmaische mit einem Feststoffgehalt von etwa 25 t anfiel. Dabei wies die Staubmaische einen auf Feststoff bezogenen Zinkgehalt von 8,3% (entsprechend etwa 2 t Zink) auf.Two electrothermal furnaces for the production of yellow phosphorus with an average total output of 75 MW enforce 1100 t of raw phosphate per day, which as foreign matter u. a. 7.5 contained 10-3% zinc. So much dust was separated out from the gas mixture consisting essentially of carbon monoxide and phosphorus vapor that daily dust mashes with a solids content of about 25 t were obtained. The dust mash had a solids-related zinc content of 8.3% (corresponding to about 2 t zinc).

Gemäß dem Blockschema nach Figur 1 wurde mit der Sinterstraße oberhalf der gestrichelten Linie (Mühle 17, Drehteller 15, Sintereinrichtung 20) Rohphosphat als Ofenrohstoff zu Phosphatpellets verarbeitet. Die Sinterstraße unterhalb der gestrichelten Linie (Mühle 24, Drehteller 22, Sintereinrichtung 28) diente zum erfindungsgemäßen Ausschleusen von Staubmaische in deponierbarer Form. Dabei wurde das mit etwa 440°C an der Sintereinrichtung 20 anfallende Kühlgas zur Trocknung des Granulates in der Sintereinrichtung 28 verwendet.According to the block diagram according to FIG. 1, crude phosphate as the raw material for the furnace was processed into phosphate pellets with the sintering line above the dashed line (mill 17, turntable 15, sintering device 20). The sintering line below the dashed line (mill 24, turntable 22, sintering device 28) was used to discharge dust mash according to the invention in a depositable form. The cooling gas obtained at the sintering device 20 at approximately 440 ° C. was used to dry the granules in the sintering device 28.

In der unteren Sinterstraße wurde in der Mühle 24 80 t entwässerte granulierte Phosphorofenschlacke auf eine Feinheit von 80% <100 µm gemahlen und mit Staubmaische auf dem Drehteller 22 granuliert. Nach dem Trocknen des Granulates auf der Sintereinrichtung 28 mit 440°C heißem Gas betrug seine Restfeuchte etwa 0,5%. Das getrocknete Granulat wurde 11 mal erneut gemahlen und mit weiterer Staubmaische granuliert und getrocknet, bis es einen Zinkgehalt von 3,6% aufwies. Danach durch das getrocknete Granulat unter Verwendung zusätzlicher Brenner auf der Sintereinrichtung 28 bei 800°C zu Pellets geglüht. Die Pellets waren frei von elementarem Phosphor und von Phosphiden.In the lower sintering mill, 24 80 t of dewatered granulated phosphorus slag were ground to a fineness of 80% <100 µm in the mill and granulated with dust mash on the turntable 22. After the granules had been dried on the sintering device 28 with gas at 440 ° C., its residual moisture was about 0.5%. The dried granulate was milled again 11 times and granulated with further dust mash and dried until it had a zinc content of 3.6%. Thereafter, annealed to pellets by the dried granules using additional burners on the sintering device 28 at 800 ° C. The pellets were free of elemental phosphorus and phosphides.

Durch die mehrmalige Verwendung des getrockneten Granulates zur erfindungsgemäßen Umsetzung mit der Staubmaische reichten die 80 t Schlacke zur Verarbeitung von 140 m3 (entsprechend 175 t) Staubmaische aus.Due to the repeated use of the dried granules for the reaction according to the invention with the dust mash, the 80 t of slag were sufficient to process 140 m 3 (corresponding to 175 t) of dust mash.

Beispiel 2Example 2

In einer Granuliertrommel von 250 I Inhalt wurde eine gemahlene Mischung von 40 kg Phosphorofenschlacke und 10 kg Kalksteinmehl (Mahlfeinheit: 80% <0,1 mm) mit Staubmaische granuliert und bei 110°C getrocknet. Das Granulat wurde gemahlen und erneut mit weiterer Staubmaische granuliert und bei 110°C getrocknet. Dieser Zyklus wurde insgesamte 14 mal durchgeführt. Schließlich wurde das getrocknete Granulat bei 800°C unter Bildung von Pellets geglüht. Die Pellets wiesen einen Zinkgehalt von 5,8% auf. Die verwendete Staubmaische hatte eine Dichte von 1,2 kg/I, einen Feststoffgehalt von etwa 30% und einen auf den Feststoff bezogenen Zinkgehalt von 13%.A ground mixture of 40 kg of phosphorus furnace slag and 10 kg of limestone powder (grinding fineness: 80% <0.1 mm) was granulated with dust mash in a granulating drum of 250 l content and dried at 110 ° C. The granules were ground and again granulated with further dust mash and dried at 110 ° C. This cycle was carried out a total of 14 times. Finally, the dried granules were annealed at 800 ° C to form pellets. The pellets had a zinc content of 5.8%. The Dust mash used had a density of 1.2 kg / l, a solids content of about 30% and a solids-based zinc content of 13%.

Beispiel 3Example 3

In die in Beispiel 2 verwendete Granuliertrommel wurden 40 kg gemahlene Phosphorofenschlacke und. 29,6 kg Filterkuchen, welcher durch Filtration von Staubmaische erhalten worden war, eingefüllt und gemischt. Die Mischung wurde mit Hilfe von Staubmaische granuliert. Das Granulat wurde bei 110°C getrocknet und anschließend bei 800°C geglüht. Die resultierenden Pellets wiesen einen Zinkgehalt von 6,1 % auf. Die verwendete Staubmaische hatte eine Dichte von 1,2 kg/I, einen Feststoffgehalt von etwa 30% und einen auf den Feststoff bezogenen Zinkgehalt von 13%.In the pelletizing drum used in Example 2, 40 kg of ground phosphor furnace slag and. 29.6 kg filter cake, which had been obtained by filtration of dust mash, filled and mixed. The mixture was granulated using dust mash. The granules were dried at 110 ° C and then annealed at 800 ° C. The resulting pellets had a zinc content of 6.1%. The dust mash used had a density of 1.2 kg / l, a solids content of about 30% and a zinc content of 13% based on the solids.

Die nach den Beispielen 1 bis 3 erhaltenen Pellets wurden einem Eluationstest mit destilliertem Wasser unterworfen (vergl. DIN 38 414 (Entwurf) Teil 4, April 1983). Die Analyse der drei Eluate ist der Tabelle zu entnehmen.

Figure imgb0001
The pellets obtained according to Examples 1 to 3 were subjected to an elution test with distilled water (see DIN 38 414 (draft) part 4, April 1983). The analysis of the three eluates is shown in the table.
Figure imgb0001

Daraus kann geschlossen werden, daß Pellets, welche unter Zusatz von Kalksteinmehl (vergleiche Beispiel 2) zur Phosphorofenschlacke erhalten wurden, eine verbesserte Deponierfähigkeit gegenüber Pellets ohne Kalksteinzusatz aufweisen (vergleiche die Beispiele 1 und 3).It can be concluded from this that pellets which have been obtained with the addition of limestone flour (see Example 2) to the phosphorus furnace slag have improved landfillability compared to pellets without the addition of limestone (see Examples 1 and 3).

Claims (12)

1. A process for purging foreign substances, in particular zinc, from the material circulation in the production of yellow phosphorus in an electrothermal furnace, ferrophosphorus and a slag, composed essentially of calcium metasilicate, in the molten form as well as a dust-containing gas mixture composed essentially of carbon monoxide and phosphorus vapor being taken off from the furnace charged with phosphate pellets, coke and pebbles, and the dust, after electrostatic separation from the gas mixture, being stirred with water to give a dust paste, and crude phosphate being processed with a mixture of dust paste and a binder, preferably a clay paste, by means of a granulating device to give moldings which are calcined in a sintering device to give phosphate pellets, which comprises grinding a part of the slag, processing the ground slag with at least a part of the dust paste by means of a granulating device to give granules, and drying the granules.
2. The process as claimed in claim 1, wherein the dried granules are ground again and the ground material is granulated with further dust paste and dried.
3. The process as claimed in claim 2, wherein compounds containing calcium oxide, preferably ground limestone and/or hydrated lime, are added to the ground material.
4. The process as claimed in any of claims 1 to 3, wherein the dried and ground granules and dust paste are granulated in a weight ratio from 6:1 to 7:1.
5. The process as claimed in claim 1, wherein filter cake obtained by filtration of dust paste is added to the part of the slag intended for grinding.
6. The process as claimed in claim 5, wherein the slag/filter cake weight ratio is from 0.5:1 to 10:1.
7. The process as claimed in claim 5, wherein compounds containing calcium oxide, preferably limestone chippings, are added to the mixture of slag and filter cake.
8. The process as claimed in any of claims 1 and 5 to 7, wherein the slag or the mixture of slag and filter cake or the mixture of slag, filter cake and compounds containing calcium oxide is ground to grain sizes of 80% <100 pm.
9. The process as claimed in any of claims 1 to 8, wherein the granules are dried at temperatures from 80 to 150°C.
10. The process as claimed in any of claims 1 to 9, wherein the ground slag or the ground mixture of slag and filter cake or the ground mixture of slag, filter cake and compounds containing calcium oxide is processed with dust paste in a weight ratio from 5:1 to 7:1 to give granules.
11. The process as claimed in any of claims 1 to 10, wherein the dried granules are calcined to form pellets, and the pellets are taken to a waste dump together with the remaining, untreated slag.
12. The process as claimed in claim 11, wherein the dried granules are calcined at temperatures from 500 to 800°C.
EP84107760A 1983-07-18 1984-07-04 Process for the elimination of foreign substances from the circulation of material in the electrothermic preparation of yellow phosphorus Expired - Lifetime EP0131848B1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3325813 1983-07-18
DE3325813 1983-07-18
DE19843404952 DE3404952A1 (en) 1983-07-18 1984-02-11 METHOD FOR REMOVING FOREIGN MATERIALS FROM THE MATERIAL CIRCUIT IN THE ELECTROTHERMAL PRODUCTION OF YELLOW PHOSPHORUS
DE3404952 1984-02-11

Publications (3)

Publication Number Publication Date
EP0131848A2 EP0131848A2 (en) 1985-01-23
EP0131848A3 EP0131848A3 (en) 1988-06-08
EP0131848B1 true EP0131848B1 (en) 1990-05-02

Family

ID=25812379

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84107760A Expired - Lifetime EP0131848B1 (en) 1983-07-18 1984-07-04 Process for the elimination of foreign substances from the circulation of material in the electrothermic preparation of yellow phosphorus

Country Status (4)

Country Link
US (1) US4537756A (en)
EP (1) EP0131848B1 (en)
CA (1) CA1207984A (en)
DE (2) DE3404952A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110330019A (en) * 2019-05-08 2019-10-15 舒爱桦 A kind of Phosphorus Slag and tail gas method of comprehensive utilization of high-efficiency environment friendly

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3637670A1 (en) * 1986-11-05 1988-05-19 Hoechst Ag METHOD FOR REMOVING METAL INGREDIENTS FROM THE ELECTROTHERMIC PRODUCTION OF DUSTS YELLOWING PHOSPHORUS
US4822583A (en) * 1987-08-17 1989-04-18 Fmc Corporation Phosphate feed material for phosphorus electric furnaces and production of same
US4806326A (en) * 1987-08-17 1989-02-21 Fmc Corporation Phosphate feed material for phosphorus electric furnace
US4783328A (en) * 1987-12-14 1988-11-08 Fmc Corporation Utilization of phosphourus containing by-products
DE3826981A1 (en) * 1988-08-09 1990-02-15 Hoechst Ag METHOD FOR PROCESSING DUST WHICH ARISES IN ELECTROTHERMAL PHOSPHORUS PRODUCTION
DE4117716A1 (en) * 1991-05-30 1992-12-03 Metallgesellschaft Ag ZINC REMOVAL FROM PHOSPHATE SLUDGE
DE4230223A1 (en) * 1992-09-10 1994-03-17 Hoechst Ag Process and plant for removing lead, cadmium and zinc from dusts
CN1092138C (en) * 1999-12-14 2002-10-09 昆明理工大学 Medium temperature vacuum method for treating mud phosphorus to extract yellow phosphorus
US8754004B2 (en) 2011-04-15 2014-06-17 The Board Of Regents For Oklahoma State University Removing phosphorus from surface and drainage waters through use of industrial by-products
CN103641090B (en) * 2013-11-18 2015-11-18 瓮福(集团)有限责任公司 High-purity yellow phosphorus production equipment and method
CN110683524A (en) * 2019-09-29 2020-01-14 贾伟 Binder, powdered rock phosphate pellet based on binder and preparation method
CN111186825A (en) * 2020-01-10 2020-05-22 郑州大学 Method for preparing sintered pellets from low-grade phosphate ore and phosphorus chemical industry waste

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1692787A (en) * 1925-02-06 1928-11-20 Ig Farbenindustrie Ag Method of purifying gases containing phosphorus
US2267077A (en) * 1939-06-13 1941-12-23 American Agricultural Chem Co Recovery of phosphorus from sludge
GB971343A (en) * 1961-12-21 1964-09-30 Albright & Wilson Mfg Ltd Production of phosphorus from ferrophosphorus
US3743700A (en) * 1971-05-13 1973-07-03 Monsanto Co Phosphorus manufacture
US3734717A (en) * 1971-11-18 1973-05-22 Fmc Corp Production of phosphorus and steel from iron-containing phosphate rock
US4420466A (en) * 1982-05-10 1983-12-13 Occidental Research Corporation Process for producing phosphorus pentoxide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110330019A (en) * 2019-05-08 2019-10-15 舒爱桦 A kind of Phosphorus Slag and tail gas method of comprehensive utilization of high-efficiency environment friendly

Also Published As

Publication number Publication date
DE3482106D1 (en) 1990-06-07
EP0131848A3 (en) 1988-06-08
DE3404952A1 (en) 1985-01-31
US4537756A (en) 1985-08-27
CA1207984A (en) 1986-07-22
EP0131848A2 (en) 1985-01-23

Similar Documents

Publication Publication Date Title
DE3013319C2 (en) Process for the production of silicon and its use in solar cells
EP0131848B1 (en) Process for the elimination of foreign substances from the circulation of material in the electrothermic preparation of yellow phosphorus
DE2501636C2 (en)
DE2719743A1 (en) BINDER COMPOSITION AND ITS USE
WO2010127669A1 (en) Method for treating cutting waste for recovering silicon for the production of solar silicon
DE112014003176T5 (en) Flux, process for its preparation, agglomeration mixture and use of a secondary metallurgy slag
DE3504346A1 (en) METHOD AND DEVICE FOR THE PRODUCTION OF SPONGE IRON AND LIQUID PIPE IRON
AT391462B (en) METHOD FOR THE PRODUCTION OF SILICON OR FERROSILICIUM IN AN ELECTRONIC LOWER STOVE AND FOR THE METHOD SUITABLE RAW MATERIALS
DE2253074C3 (en) Process for the pyrometallurgical treatment of solids
EP0526697B1 (en) Method and apparatus for treating mineral wool wastes
DE69702349T2 (en) &#34;WAELZ&#34; METHOD FOR PROCESSING ZINC CONTAINING RAW MATERIALS ON PELLETED FORM
DE3811594C2 (en)
DE2314637C2 (en) Process for the pre-granulation of industrial dust separated in dedusting systems
DE1300911C2 (en) Process for the production of phosphate pellets
DE4123626A1 (en) Reconditioning metallurgical residues with reduced installation costs - involves agglomeration or pelleting of residues, supplying to counted-flow melting unit with dust filter, heating and drying, etc.
DE3413664C2 (en)
DE69801157T2 (en) METHOD FOR RECYCLING WASTE MATERIALS FROM THE BRASS FOUNDRY
EP0586910B1 (en) Process and installation for removing lead, cadmium and zinc from dusts
DE1927687B2 (en) PROCESS FOR THE MANUFACTURING OF PHOSPHATE BRIQUETTES
EP2662457A1 (en) Method and apparatus for the production of agglomerates and using the agglomerates in a FINEX ® process
EP0097144B1 (en) Process for separating non ferrous metals from residues containing iron oxide
AT407039B (en) METHOD FOR CLEANING PROCESS WATERS
DE3827782A1 (en) PHOSPHATE FEEDING FOR ELECTROOFEN FOR THE PRODUCTION OF PHOSPHORES AND METHOD FOR THE PRODUCTION THEREOF
DE941392C (en) Process for the extraction of zinc from oxidic zinc-containing material with carbon-containing reducing agents in an electric arc furnace
DE4006651C1 (en) Treating used lead batteries - by breaking into pieces, placing on inclined conveyor, collecting sulphuric acid in vessel and neutralising

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): DE FR GB NL

17P Request for examination filed

Effective date: 19841212

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB NL

17Q First examination report despatched

Effective date: 19891017

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB NL

ET Fr: translation filed
REF Corresponds to:

Ref document number: 3482106

Country of ref document: DE

Date of ref document: 19900607

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19920611

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19920615

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19920731

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19920921

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19930704

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19940201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930704

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19940331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19940401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST